Process for the polymerization of allyl halides

ABSTRACT

Allyl halides are polymerized by a catalyst, silicic or silicoformic acids, to produce poly(allyl halide) polymer and poly(allyl alcohol) polymer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of my copending U.S. Patentapplication, Ser. No. 551,534, filed Feb. 21, 1975, which is acontinuation-in-part of my earlier U.S. Patent application, Ser. No.71,628, filed Sept. 11, 1970, now abandoned.

BACKGROUND OF THE INVENTION

This invention relates in general to the process for the polymerizationof allyl halides by using silicic acids, silicoformic acid, or acombination of silicic acid and silicoformic acid as the catalyst and,more specifically, to a process for producing novel poly(allyl chloride)polymer, poly(allyl alcohol) polymer and poly(allyl silicoformate)polymer.

Silicoformic acid may be produced by the chemical reaction of a dry,granular alkali metal metasilicate or an alkaline earth metalmetasilicate with a mineral acid or a hydrogen salt. The silicoformicacid is washed with water to remove the salt, then filtered and airdried into a fine white granular compound. Silicoformic acid, also knownas monosilanic acid, has the general formula H.SiO.OH. It can also beproduced by other methods, such as those disclosed in U.S. Pat. No.3,674,430.

The metasilicic acid, orthosilicic acid and gelatinous silicic acid maybe produced by any of the commonly known methods, such as treating anaqueous solution of sodium silicate with an acid to produce a gelatinoussilicic acid or treating clay with sulfuric acid to produce metasilicicacid.

Allyl halides may be produced by the addition of a halide to propylene.Methallyl chloride may be produced by the addition of a halide toisobutylene. Other compounds with the combination C=C--C, which is knownas the allylic system, may be used. Allyl chloride is the preferredallyl halide. Other allyl halides such as allyl bromide and methallylchloride may be used in this process.

Poly(allyl halide) polymer, poly (allyl alcohol) polymer and poly(allylsilicoformate) polymer may be used as coating agents, adhesives,impregnants, molding powders, paints, varnishes, laminates, fillers, indispersions and as an intermediate in resin production.

Poly(allyl halide) polymer and poly(allyl alcohol) polymer willchemically react with silicoformic acid by heating the mixture in thepresence of an alkali catalyst to produce poly(allyl silicoformate)polymer ##STR1## Poly(allyl silicoformate) polymer may also be producedby adding an alkali hydroxide to the allyl chloride and silicoformicacid mixture.

Poly(allyl alcohol) polymer may be chemically reacted with a dicarboxylacid or an anhydride to produce a polyester resin. Poly(allyl alcohol)polymer may be chemically reacted with a diisocyanate to produce apolyurethane resin or foam.

By using this process, allyl chloride may be copolymerized with otherpolymerable organic compounds by using an acetic or basic catalyst.Allyl chloride, when mixed with silicic acid or silicoformic acid, willpolymerize in a wide range of pH, from a pH of 2 to 11; therefore bothbasic and acetic catalysts may be used with silicic acid or silicoformicacid to copolymerize allyl chloride with other polymerable organiccompounds. Acrylic acid may be copolymerized with allyl chloride andsilicoformic acid with an alkali catalyst to produce a clear poly(allylchloride acrylic silicoformate) polymer which is soluble in dilutealkali aqueous solutions.

Allyl chloride may be copolymerized with polymerable organic compoundsby adding an alkali aqueous solution and a peroxide to the silicic orsilicoformic acid. A redox system may be used for the copolymerizationby adding silicic or silicoformic acid as the catalyst or allylchloride. Allyl chloride may be copolymerized with vinyl chloride, vinylacetate, acrylonitrile, acrylic acid, methacrylic acid, methyl acrylate,methyl methacrylate, vinylidene chloride, isoprene, chloroprene,butadiene, styrene, methyl styrene and other polymerable organiccompounds.

Poly(allyl chloride) polymer may be chemically reacted with an alkalihydroxide or carbonate in an aqueous or alcoholic solution to produce apoly(allyl alcohol) polymer ##STR2## Poly(allyl alcohol) polymer isproduced when allyl chloride is mixed with silicic acid or silicoformicacid, water and an alkali. The chemical reaction proceeds rapidly atambient temperature and pressure. About 80-90% of the allyl chloride ispolymerized in about one hour. The poly(allyl alcohol) polymer will forman emulsion with water and then gradually separates out as a creamcolored, soft, sticky polymer.

While the specific reactions to produce poly(allyl alcohol) polymer arenot fully understood, typical reactions which are believed to occur takeplace as follows: ##STR3## There is also a mixture of poly(allylchloride) polymer and poly (allyl alcohol) polymer present; not all ofthe poly(allyl chloride) polymer is converted to poly(allyl alcohol)polymer. There is also a small percent of poly(allyl silicoformate)polymer produced when silicoformic acid is used as the catalyst.

Allyl chloride will also copolymerize with other allyl compounds such asallyl alcohol, methallyl chloride and allyl bromide by using a siliconacid catalyst.

DETAILED DESCRIPTION OF THE INVENTION

Any suitable allyl halide compound with the combination C=C--C, known asthe allylic system, may be used in my novel process. Typical allylhalide compounds are allyl chloride, methallyl chloride and allylbromide.

Any suitable silicic acid, silicoformic acid or combinations of silicicacids, silicoformic acid and silicon dioxide may be used as the catalystin this invention. The catalytic mechanism which takes place is notfully understood. The silicic acid and siliconformic acid may reactslightly with one of the primary reactants. When an alkali compound isadded to the silicic acid and silicoformic acid and heated, it willreact with the primary reactant. The amount of silicic acid orsilicoformic acid needed to catalyze the reaction may vary greatly, from1% to 50% by weight. The preferred concentration is 1 part silicon acidto 2 parts allyl halide by weight to initiate the polymerization, thenmore allyl halide may be gradually added, and the polymerizationcontinues.

The poly(allyl chloride) polymer produced by my novel process may bechemically reacted with alkali compounds to produce a mixture ofpoly(allyl chloride) and poly(allyl alcohol) polymer. The poly(allylchloride) polymer may be reacted with silicoformic acid by using asuitable alkali catalyst and heat to produce a tan soft solid poly(allylsilicoformate) polymer.

The poly(allyl alcohol) polymer produced by my novel process may bechemically reacted with carboxylic acids and dicarboxylic acids toproduce new condensation resins.

DESCRIPTION OF PREFERRED EMBODIMENTS

The following examples describe in detail certain preferred embodimentsof the process of my invention. These preferred processes may, ofcourse, be varied as described with similar results. Parts andpercentages are by weight unless otherwise indicated.

EXAMPLE I

About 3 parts by weight of sodium metasilicate pentahydrate are slowlyadded to about 2 parts by weight of concentrated sulfuric acid whileagitating and keeping the temperature below 100° C. Oxygen is given offand considerable heat is produced. The chemical reaction is complete in2-6 hours, thereby producing silicoformic acid and sodium sulfate. Thesilicoformic acid (H.SiO.OH) is washed with water and filtered to removethe sodium sulfate, then air dried into a white granular compound.

About 1 part by weight of fine granular silicoformic acid and about 2parts by weight of allyl chloride are mixed together and agitated forabout 20 to 40 minutes at a temperature of between 0° and 45° C andambient pressure, thereby producing a thick, light, yellow liquid,poly(allyl chloride) polymer. The polymer becomes a soft solid polymerin 6 to 12 hours.

About 4 parts by weight of allyl chloride are added to the mixture ofsilicoformic acid and poly(allyl chloride) polymer. The polymer goesinto solution and is filtered off. The solution is then heated to abovethe boiling point of allyl chloride to remove the solvent, therebyrecovering poly(allyl chloride) polymer. The allyl chloride which isevaporated may be recycled through the silicoformic acid.

EXAMPLE II

Dilute sulfuric acid is added to a solution of sodium silicate (waterglass) until the pH is 6 to 7, thereby producing gelatinous silicicacid. The water and salt are filtered off; the gelatinous silicic acidis then rewashed with water, filtered and air dried at 60° to 100° C.

About one part by weight of dried, granular, gelatinous silicic acid andabout one part by weight of allyl chloride are mixed then agitated atambient temperature and pressure for 15 to 40 minutes. About one partallyl chloride is added to the mixture and agitated for 15 to 20minutes, then another one part by weight of allyl chloride is added tothe said mixture, mixed and agitated for 30 to 40 minutes, therebyproducing a thick, light yellow polymer, poly(allyl chloride) polymer.The mixture becomes a soft, solid mass in 6 to 12 hours. About 5 partsby weight of water are added to the mixture and agitated, therebyseparating the poly(allyl chloride) polymer from the silicic acid. Thewater and polymer are filtered off the silicic acid. The polymerseparates from the water, and the water is filtered off, therebyrecovering the poly(allyl chloride) polymer.

EXAMPLE III

Allyl chloride is continuously passed through a column of silicoformicacid granules at a slow rate which requires about 30 to 90 minutes for agiven amount to pass through this column. About 60 to 80% of the allylchloride that passes through the column of silicoformic acid ispolymerized and the unpolymerized allyl chloride acts as the solvent,thereby removing the poly(allyl chloride) polymer from the column ofsilicoformic acid into another suitable vessel. The allyl chloride isevaporated by heating the solution to above the boiling point of allylchloride, thereby recovering poly(allyl chloride) polymer, a thick,light yellow, liquid. The allyl chloride monomer is then recycledthrough the column of silicoformic acid.

EXAMPLE IV

About 2 parts by weight of allyl chloride are mixed with about one partof a catalyst containing about equal parts of silicoformic acid,orthosilicic acid and metasilicic acid. The mixture is agitated andheated to about 35° to 100° C in a closed system at ambient pressure forabout 15 to 30 minutes, thereby polymerizing the allyl chloride andproducing poly(allyl chloride) polymer. The poly(allyl chloride) polymeris removed from the catalyst with a solvent such as acetone. Thepoly(allyl chloride) polymer is recovered by evaporating the acetone.

EXAMPLE V

About 2 parts by weight of allyl chloride are mixed with about 1 part byweight of granular silicoformic acid. The mixture is agitated for 15 to30 minutes at ambient temperature and pressure. Additional 10 parts byweight of allyl chloride are added in proportions of 2 parts asdescribed above, thereby producing a thick liquid, poly(allyl chloride)polymer, which after 6 to 12 hours becomes a soft, solid polymer. Thepolymer is recovered by mixing the mixture with a solvent, methylenechloride and filtered from the silicoformic acid. The solvent isevaporated, thereby recovering poly(allyl chloride) polymer. Thisprocess may be carried out at a temperature between 0° and 100° C.

EXAMPLE VI

About 20 parts by weight of gelatinous othosilicic acid containing about40 parts by weight of water are mixed with about 20 parts by weight ofgranular sodium carbonate and about 20 parts by weight of sodiumhydroxide flakes. About 40 parts by weight of allyl chloride are addedto the said mixture, agitated at ambient temperature and pressure for 20to 40 minutes, thereby producing a thick, cream colored polymer,poly(allyl alcohol) polymer.

The poly(allyl alcohol) polymer continues to polymerize and becomes asoft solid polymer in 6 to 12 hours. About 100 parts by weight of waterare added to the mixture and agitated for about 5 to 10 minutes. Thepoly(allyl alcohol) polymer emulsifies and is filtered from the silicicacid. Upon sitting for a few minutes, the poly(allyl alcohol) polymerseparates from the water and is recovered by removing the water.

EXAMPLE VII

About 10 parts by weight of allyl chloride, about 5 parts by weight ofsilicoformic acid and about 5 parts by weight of sodium hydroxide flakesare mixed, then agitated at 30° to 40° C and ambient pressure for 20 to40 minutes. About 50 parts by weight of water is added to said mixtureand mixed. A thick, tan colored liquid polymer floats to the top and isremoved, thereby recovering poly(allyl silicoformate) polymer.

EXAMPLE VIII

About 10 parts by weight of allyl chloride and about 5 parts by weightof silicoformic acid are mixed, then agitated for 20 to 40 minutes,thereby producing a thick, light yellow liquid polymer, poly(allylchloride). About 8 parts by weight of sodium carbonate are mixed withthe silicoformic acid and poly(allyl chloride) mixture, then heated to40° to 80° C at ambient pressure for 20 to 40 minutes, thereby producinga tan, solid polymer, poly(allyl silicoformate) polymer. The salt andsodium hydrogen carbonate are removed by washing and filtering.

EXAMPLE IX

About 10 parts by weight of allyl chloride, about 10 parts allylalcohol, about 5 parts by weight of potassium carbonate, about 10 partssilicoformic acid and about 10 parts by weight of water are mixed thenagitated at ambient temperature and pressure for 30 to 60 minutes,thereby producing a cream colored, thick, liquid copolymer, poly(allylchloride allyl alcohol). The copolymer becomes a soft, solid copolymerafter 6 to 12 hours. The copolymer is separated from the catalyst,silicoformic acid, by adding 100 parts by weight of water. The copolymerfloats to the top and is removed from the water, thereby recoveringpoly(allyl chloride allyl alcohol) copolymer.

EXAMPLE X

About 20 parts by weight of allyl chloride, about 10 parts by weight ofgranular orthosilicic acid, about 5 parts by weight of sodium carbonateare mixed, then agitated for 20 to 50 minutes at ambient temperature andpressure, thereby producing a cream colored, thick, liquid copolymer,poly(allyl chloride allyl alcohol). The copolymer is extracted from thesilicic acid by a solvent, allyl chloride monomer.

Although specific materials and conditions were set forth in the aboveExamples, these were merely illustrative of preferred embodiments of myinvention. Various other compositions, such as the typical materialslisted above may be used, where suitable. The reactive mixture andproducts of my invention may have other agents added thereto to enhanceor otherwise modify the reaction and products.

Other modifications of my invention will occur to those skilled in theart upon reading my disclosure. These are intended to be included withinthe scope of my invention, as defined in the appended claims.

I claim:
 1. The process for the production of poly(allyl halide) polymerwhich comprises the steps of:a. providing a quantity of silicon acid; b.mixing therewith an allyl halide in the ratio of 1 part by weight ofsilicon acid to 2 parts by weight of an allyl halide, c. agitating saidmixture in a closed system and keeping the temperature between 0° and100° C for about 20 to 40 minutes at ambient pressure; thereby d.producing poly(allyl chloride) polymer.
 2. The process according toclaim 1 wherein the silicon acid is chosen from the group oforthosilicic acid, metasilicic acid, gelatinous silicic acid,silicoformic acid or mixtures thereof.
 3. The process according to claim1 wherein the silicon acid is silicoformic acid.
 4. The processaccording to claim 1 wherein the allyl halide is allyl chloride.
 5. Theprocess according to claim 1 wherein the allyl halide is allyl bromide.6. The process according to claim 1 including the further steps of:a.dissolving poly(allyl halide) polymer with a solvent, allyl chloridemonomer; b. filtering the solvent and poly(allyl halide) polymer fromthe silicon acid, c. recovering poly(allyl halide) polymer by heatingthe solvent, allyl chloride, to above the boiling point, then d.evaporating allyl chloride from the poly(allyl halide) polymer.